CN106797029B - Cathode active material for lithium secondary battery, preparation method and the lithium secondary battery comprising it - Google Patents

Cathode active material for lithium secondary battery, preparation method and the lithium secondary battery comprising it Download PDF

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CN106797029B
CN106797029B CN201580054001.7A CN201580054001A CN106797029B CN 106797029 B CN106797029 B CN 106797029B CN 201580054001 A CN201580054001 A CN 201580054001A CN 106797029 B CN106797029 B CN 106797029B
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lithium
particle
cobalt oxides
positive electrode
electrode active
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CN106797029A (en
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赵治皓
柳志勋
姜玟锡
申先植
郑王谟
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LG Energy Solution Ltd
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LG Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of cathode active material for lithium secondary battery, it includes lithium and cobalt oxides particles, wherein the lithium and cobalt oxides particle include on the surface of the particle on sum corresponding to the lithium and cobalt oxides for starting poor lithium from the region of 0% to less than 100% distance from the surface of the particle relative to the distance (r) from the surface of the particle to center, the lithium and cobalt oxides of the poor lithium have Li/Co molar ratio less than 1, belong to Fd-3m space group and with cube type crystal structure.Cathode active material for lithium secondary battery according to the present invention promotes the insertion and deintercalation of the lithium at particle surface, to improve output characteristics and multiplying power property when being applied to battery.Therefore, it even if when positive electrode active materials are big particle, also show excellent life characteristic and the amount of the gas generated can be made to minimize.

Description

Cathode active material for lithium secondary battery, preparation method and comprising its lithium it is secondary Battery
Technical field
Cross-reference to related applications
The Korean Patent Application No. 2014-0133428 and 2014-0133429 submitted this application claims on October 2nd, 2014 And the equity of the priority of Korean Patent Application No. 2015-0138746 that on October 1st, 2015 submits, it is special in corresponding South Korea Full content described in the disclosure of benefit application is incorporated herein in this as a part of this specification.
Technical field
Just the present invention relates to cathode active material for lithium secondary battery, preparation method and comprising the secondary lithium batteries The lithium secondary battery of pole active material.
Background technique
With the continuous growth of technological development and demand to mobile device, the demand to the secondary cell as the energy is just Rapid growth.In the secondary battery, with the secondary electricity of lithium of high-energy density and voltage, long circulation life and low self-discharge rate Pond is commercialized and is widely used.
However, the defect of lithium secondary battery is, service life repeated charge and discharge and quickly reduce.Particularly, the defect It is more serious at high temperature.The reason is that, electrolyte may be decomposed due to the moisture or other factors in battery, active material can It can deteriorate or the internal resistance of battery can increase.
The cathode active material for lithium secondary battery just actively studied, developed and used is with layer structure LiCoO2。LiCoO2It can be easily synthesized, and there is the good chemical property comprising life performance, and be most extensively The material used.However, LiCoO2With low structural stability, it is applied to the battery with high capacity and is restricted.
As the substitute of positive electrode active materials, various lithium transition-metal oxides such as LiNiO has been developed2、 LiMnO2、LiMn2O4Or LiFePO4。LiNiO2Have the advantages that provide the battery performance of high discharge capacity, however it is difficult to pass through Simple solid state reaction kinetics, and there is low thermal stability and cycle performance.In addition, lithium manganese oxide such as LiMnO2Or LiMn2O4Has the advantages that good thermal stability and at low cost, however it is with small and performance difference at high temperature the defect of capacity. Specifically, for LiMn2O4For, some products can be with low cost commercialization；However its life performance is due to because of Mn3+Cause Jahn-Teller deformation and it is bad.Because of LiFePO4Cheap and safety, therefore to be used for hybrid electric vehicle (HEV) numerous studies are being carried out, however due to electric conductivity is low, it is applied to other fields and is difficult.
Given this situation, lithium-nickel-manganese-cobalt oxide Li (NixCoyMnz)O2(wherein x, y and z are each independent oxidation The atomic fraction of object constitution element, and meet 0 < x≤1,0 < y≤1,0 < z≤1 and 0 < x+y+z≤1) it is used as LiCoO2Replace It is concerned for property positive electrode active materials.Material ratio LiCoO2It is cheap and have and to be used under high capacity and high voltage Advantage.However, the material has the shortcomings that not providing good multiplying power property and life performance at high temperature.In order to increase lithium nickel The structural stability of manganese cobalt/cobalt oxide increases the amount of the Li of the amount relative to the transition metal for including in oxide.
Recently, as the size of mancarried device such as mobile phone and tablet computer gradually minimizes, electricity applied by it is needed Pond is also minimized with high capacity and high-energy in the case where.In order to increase the energy of per unit volume battery, need to increase The bulk density of active material.In order to increase bulk density, preferably there is large-sized active material.However, having large scale Active material there is relatively small surface area, therefore the effective area contacted with electrolyte may be also small.Small is effective Area may be kinetically unfavorable, and be likely to be obtained relatively low multiplying power property and initial capacity.
Summary of the invention
Technical problem
According to the first aspect of the invention, cathode active material for lithium secondary battery is provided, wherein can be easily in grain The insertion and deintercalation that lithium ion is carried out at the surface of son, can improve output performance when being applied to battery and multiplying power is special Property, even if life performance can also be improved in case of large particle size, and the amount of the gas generated can be made to minimize.
According to the second aspect of the invention, the method for preparing the positive electrode active materials is provided.
According to the third aspect of the invention we, the anode comprising the positive electrode active materials is provided.
According to the fourth aspect of the invention, lithium secondary battery, battery module and battery pack comprising the anode are provided.
Technical solution
An embodiment according to the present invention for being used to complete above-mentioned task, provides the lithium comprising lithium and cobalt oxides particle Cathode active material for secondary battery, wherein the lithium and cobalt oxides particle include on the surface of the particle on sum correspond to phase 0%~distance less than 100% is started from the surface of the particle for the distance (r) from the surface of the particle to center The lithium and cobalt oxides of poor lithium in region, the lithium and cobalt oxides of the poor lithium have Li/Co molar ratio less than 1, belong to Fd-3m Space group and have cube type crystal structure.
According to another implementation of the invention, the preparation method of cathode active material for lithium secondary battery, institute are provided The method of stating includes: by mixing cobalt raw material and lithium raw material, and the first heating of progress with the amount for meeting the molar ratio of 1≤Li/Co And prepare the second lithium and cobalt oxides particle；It is heated with more than one second is carried out to the second lithium and cobalt oxides particle.
Another embodiment according to the present invention is providing the secondary lithium batteries comprising the positive electrode active materials just Pole.
In addition, another embodiment according to the present invention, provides lithium secondary battery, battery module comprising the anode And battery pack.
By the details comprising exemplary embodiments of the present invention in following detailed description.
Beneficial effect
Cathode active material for lithium secondary battery according to the present invention has included in the surface of the active material particles Poor lithium structure on side can be easy to carry out the insertion and deintercalation of lithium ion by the poor lithium structure, and can increase The transmission rate of lithium ion, to improve multiplying power property when being applied to battery.Furthermore, it is possible to reduce on the surface of active material The impedance at place, and volumetric properties can be improved and be not concerned about the deterioration of initial capacity.In addition, even if large scale particle feelings Also good life performance may be implemented under condition, simultaneously as the increase of the density of anode, can improve the energy density of battery. Therefore, cathode active material for lithium secondary battery according to the present invention can be particularly easy to the high voltage as 4.4V or more The positive electrode active materials of battery.
Detailed description of the invention
Attached drawing in present disclosure shows the preferred embodiment of the present invention, and with explanation together for further managing Solve the principle of the present invention.The present invention should not be construed as limited to the explanation in attached drawing.
Fig. 1 is shown using in the positive electrode active materials prepared in atom-probe sectional analysis art (APT) observation preparation example 2 The photography photo of lithium distribution in the surface side of particle；
Fig. 2 shows the crystal for the positive electrode active materials for using transmission electron microscope (TEM) observation to prepare in preparation example 2 The photography photo of structure；
Fig. 3 is that the lithium secondary batteries of the positive electrode active materials comprising preparing in preparation example 1 and comparative example 1 is shown respectively to fill The figure of initial charge/discharge performance during electric discharge；And
Fig. 4 is that the lithium secondary batteries of the positive electrode active materials comprising preparing in preparation example 1 and comparative example 1 is shown respectively to fill The figure of high rate performance during electric discharge.
Specific embodiment
Hereinafter, the present invention will be described in more detail to help to understand the present invention.
It will be further understood that, term and word used in the specification and claims should not be interpreted as having for example The usually used or meaning defined in dictionary, but should be in inventor in order to explain his invention in the best manner And on the basis of suitably defining the principle of the concept of term, be construed to the meaning that is consistent with technology purport of the invention and Concept.
In general, the multiplying power property of positive (positive electrode) active material depends on positive electrode active materials The rate of interfacial reaction between electrolyte.The present invention can be with by forming poor lithium structure in the preparation of positive electrode active materials Improve multiplying power property when being applied to battery, it can be at the outside of lithium and cobalt oxides particle, i.e. table by the poor lithium structure It is easy to carry out the insertion and deintercalation of lithium ion at surface side, and the three-dimensional transmission of lithium ion can be carried out.In addition, due in work Property material particles surface at impedance reduce, therefore output performance can be improved.Therefore, even if positive electrode active materials have greatly Sized particles can also obtain good life performance, and the increase of the density due to anode, can improve the energy of battery Density.
That is, the cathode active material for lithium secondary battery of embodiment according to the present invention includes lithium and cobalt oxides particle.
The lithium and cobalt oxides particle is included in the surface side of the particle, is i.e. in the surface of the particle and corresponding In being started from the surface of the particle from 0% to less than 100% relative to the distance (r) from the surface of the particle to center The lithium and cobalt oxides of poor lithium in the region of distance, the lithium and cobalt oxides of the poor lithium are with the Li/Co molar ratio less than 1, category In Fd-3m space group and there is cube type crystal structure.
Specifically, in the positive electrode active materials of embodiment according to the present invention, the lithium and cobalt oxides particle includes Li/Co molar ratio in the surface side of the particle less than 1, more specifically 0.95~the lithium cobalt oxidation of poor lithium less than 1 Object.
Different from the common lithium and cobalt oxides with layered crystal structure, the lithium and cobalt oxides of the poor lithium can have category In cube type crystal structure of Fd-3m space group, and its lattice constant (a0) can be 7.992~7.994 (25 DEG C).The crystalline substance Body structure is similar to spinel type crystal structure, and lithium ion can be as in spinel type crystal structure in three-dimensional side Transmission upwards.It, can be with when therefore, compared with the situation in the layer structure that can be transmitted in the two-dimensional direction with wherein lithium ion Be easy to carry out the transmission of lithium ion, and rate can be it is fast, so that the insertion and deintercalation of lithium ion can become more to hold Easily.In the present invention, the lithium and cobalt oxides of the poor lithium with above-mentioned crystal structure and advantageous mechanical performance are arranged in the grain In the surface side of son, and lithium ion can be easy to carry out transmission, and can improve multiplying power property when being applied to battery. In addition, the impedance due to the surface side in active material reduces, it is possible to improve output performance.
The crystal structure of the lithium and cobalt oxides of poor lithium can be identified by the common identification method of crystal structure, and be had Body, transmission electron microscope can be used to identify in crystal structure.
More specifically, the lithium and cobalt oxides of poor lithium may include the first lithium and cobalt oxides of following formula 1.
[formula 1] Li1-aCoMxO2
In formula 1, a and x are the atomic fraction of each independent oxide constitution element and meet following relationship: 0 < a≤ 0.05 and 0≤x≤0.02.)
In formula 1, M includes selected from least one of W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, Cr, Ba, Ca and Nb metal Element as doped chemical, and can with so that x meet relational expression 0≤x≤0.02 amount be included in the first lithium and cobalt oxides In.As described above, stable structure can be improved in the case where in the lithium and cobalt oxides that metallic element is further doped to poor lithium Property, and no longer there is the worry of the deterioration to the structural stability of the positive electrode active materials as caused by poor lithium.Furthermore it is possible to Improve the output performance of battery, and by adulterating above-mentioned amount, can further improve its improvement.
More specifically, in the cathode active material for lithium secondary battery of embodiment according to the present invention, lithium cobalt oxidation Object particle can have nucleocapsid structure.In this case, shell portion may include the first lithium and cobalt oxides of poor lithium of following formula 1, and Core portion may include the second lithium and cobalt oxides of following formula 2.
[formula 1] Li1-aCoMxO2
[formula 2] LibCoM’yO2
(in formula 1 and 2, M and M ' each independently comprising selected from W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, Cr, Ba, Ca and At least one of Nb metallic element, and a, b, x and y be each independent oxide constitution element atomic fraction, and meet with Lower relational expression: 0 < a≤0.05,1≤b≤1.2,0≤x≤0.02, and 0≤y≤0.02.)
In formula 1, while meeting two relational expression 0 < a≤0.05 and 1≤b≤1.2, when being greater than 0.05 with " a " and " b " is greater than When 1.2 active material is compared, the improvement of the multiplying power property as caused by the formation of poor lithium structure can further improve 10% or more.As the lithium and cobalt oxides (LiCoO with not formed poor lithium structure2) compared to when, the improvement of multiplying power property can be with Improve maximum 30%.
In lithium and cobalt oxides particle, the first lithium and cobalt oxides can have spinelle shape structure as described above To belong to Fd-3m space group, there are cube type crystal structure and the second lithium and cobalt oxides can have layer structure.
As described above, the transmission about lithium ion, the positive electrode active materials of embodiment according to the present invention include to have It can make lithium ion in the surface side of active material particles, carry out the defect sturcture (defect of three-dimensional transmission in shell portion Structure lithium and cobalt oxides), and the transmission of lithium can become easy, the initial cells internal resistance of lithium secondary battery can be with It reduces, and the multiplying power property of battery and output performance can be improved.In addition, by the inside of active material particles, The structural stability of active material can be improved than the lithium and cobalt oxides of the rich lithium for 1 or more comprising Li/Co i.e. in core portion, Especially its structural stability at high temperature, and can prevent capacity from deteriorating at high temperature.Such effect is big to having The positive electrode active materials of sized particles can be more effectively.
In view of being controlled according to the position in active material particles, Li/Co is when thus obtained to significantly improve effect Fruit can meet 0.01 < a≤0.05 and 1≤b≤1.05 two relational expression in formula 1 and 2.
More specifically, core portion and shell portion can be in respective region Zhong Bao in the positive electrode active materials with nucleocapsid structure Containing the lithium being distributed towards the center of active material particles with the concentration gradient gradually increased.
In this case, lithium concentration gradient slope (the lithium concentration in core portion and shell portion Gradient slope) it can be formed with the thickness for the particle started from the center of active material particles and be become each independently The linear equation of change, or can be quadratic equation.In addition, the lithium concentration gradient in lithium concentration gradient slope and shell portion in core portion The gradient can have identical or different value of slope.
Meanwhile in the positive electrode active materials with nucleocapsid structure, core portion and shell portion can be respectively contained in respective region In with lithium existing for a concentration value.It in this case, include that lithium concentration in core portion can be higher than and be included in shell portion Lithium concentration.
In addition, in the case where core portion and shell portion have different lithium concentration distributions each independently, in core portion and shell portion Contact interface at can form the difference in height based on the lithium concentration difference in core portion and shell portion.
Meanwhile the positive electrode active materials with nucleocapsid structure may be embodied in entire active material particles from particle The lithium for the concentration gradient distribution that surface is gradually increased to center.In this case, in formula 1 and 2, a can 0 < a≤ Reduce in the range of 0.05 towards the center of particle, and b can increase in the range of 1≤b≤1.2 towards the center of particle. In addition, lithium concentration gradient slope can be each independently with the thickness for the particle started from the center of active material particles and The linear equation of variation, or can be quadratic equation.Using the concentration gradient in entire particle, from center to face, there is no anxious Fast phase boundary regions (rapid phase boundary region), to keep crystal structure stable and increase thermal stability.Separately Outside, if the concentration gradient gradient of metal be it is constant, the improvement of structural stability can be further increased.
In the present invention, the concentration of the surface of particle and the lithium in inside variation can be measured by commonsense method, specifically The concentration of ground, lithium present in surface and other elements can pass through x-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) or X-ray energy dispersion spectrum (EDS) measures.Inductively coupled plasma can be used in lithium ingredient in lithium and cobalt oxides Body-Atomic Emission Spectrometer AES (ICP-AES) is measured, and the shape of lithium and cobalt oxides can be used the flight time it is secondary from Sub- mass spectrograph (ToF-SIMS) is identified.
In the present invention, " surface side " of lithium and cobalt oxides particle refers to the surface of particle and excludes the table at the center of particle The adjacent area in face, and specifically refer to correspond to distance from the surface of lithium and cobalt oxides particle to center, i.e. relative to lithium cobalt The radius of oxide is started from the surface of particle from 0% to the region of the distance less than 100%.In addition, lithium and cobalt oxides particle Shell portion be corresponding to from the surface of lithium and cobalt oxides particle to center distance, i.e. relative to the radius of particle from the table of particle Start the region of from 0% to 99% distance, more specifically from 0% to 95% distance in face.Therefore, core portion is present in shell portion Inside, and refer to from lithium and cobalt oxides particle exclude shell portion region.
Specifically, in lithium and cobalt oxides particle, the radius in core portion and the thickness in shell portion can have 1:0.01~1:0.1 Thickness ratio.The radius in core portion deviate above-mentioned ratio ranges and it is excessive in the case where, due to the lithium and cobalt oxides comprising poor lithium Shell portion formation caused by lithium ion ambulant increase effect and thus obtained battery performance improvement may Inappreciable, and the thickness in shell portion deviate above-mentioned thickness ratio and it is blocked up in the case where, core portion opposite may be reduced, and And the structure stabilization effect in active material particles may be inappreciable.More specifically, the core portion radius with Under conditions of the thickness ratio in shell portion, the thickness in shell portion can be 1nm~500nm or 10nm~450nm.
In the cathode active material for lithium secondary battery of embodiment according to the present invention, relative to positive electrode active materials The content ratio of total weight, the second lithium and cobalt oxides with poor lithium structure can be 10 weight of weight %~30 %.If the The amount of two lithium and cobalt oxides is less than 10 weight %, then the improvement as caused by the formation of poor lithium structure may be insignificant , and if the amount of the second lithium and cobalt oxides is greater than 30 weight %, capacity is likely to reduced, and structure may collapse.
In the present invention, the content of the second lithium and cobalt oxides with poor lithium structure can obtain in the following way: logical The poor Li structure in surface in the analysis identification shell using TEM is crossed, determines its thickness by total volume ratio confirmation mass ratio；Or it is logical Under type such as is crossed to obtain: during icp analysis in weak acid by control dissolution time from surface dissolving lithium cobalt bit by bit Oxide particle by the ratio of filtrate analysis Li/ transition metal (such as Co), and measures the weight of not molten part.
The positive electrode active materials of embodiment according to the present invention are whole with being formed by the primary particle of lithium and cobalt oxides Body structure (monolith structure).
In the present invention, " overall structure " refers to the wherein particle existing for the independent phase do not reunited each other on morphology Structure.It may include the physics of the particle (primary particle) by relative small size with the particle structure of overall structure in contrast And/or chemical agglomeration forms the structure of relatively large-sized shape of particle (secondary).
In general, the size of the particle of positive electrode active materials be preferably it is big to obtain high battery capacity, however In this case, since surface area is relatively small, existing causes again since the effective area contacted with electrolyte is reduced The problem of rate characteristic and initial capacity deteriorate.In order to solve the defect, the main primary particle using by aggregation fine particle The positive electrode active materials of the secondary phase of acquisition.However, in the positive electrode active materials with the second particle of graininess, lithium from Son may while mobile to the surface of active material with the moisture or CO in air2Reaction, so that surface easy to form is miscellaneous Matter such as Li2CO3And LiOH, and the surface impurity being consequently formed may be decreased the capacity of battery or may decompose in the battery and Gas is generated, to cause the expansion of battery.Therefore, the stability under high temperature may become severe.However, according to the present invention The positive electrode active materials of embodiment have overall structure, therefore do not have to concern the positive-active material for generating and having secondary phase The defect of material.
In view of the specific surface area and density of cathode mix, there are integrally-built positive electrode active materials can have 3 μ Average grain diameter (the D of m~50 μm50), and due to enabling lithium ion to be easily embedded into the architectural characteristic with deintercalation, can have There is 10 μm~50 μm of larger average grain diameter (D50)。
In the present invention, the average grain diameter (D of lithium and cobalt oxides particle50) can be by 50% based on size distribution at Partial size limits.Average grain diameter (the D of lithium and cobalt oxides particle50) such as laser diffractometry can be used to measure, especially by Following measurement: in a dispersion medium by the dispersion of lithium and cobalt oxides particle, it is introduced into commercial laser diffraction particle measurement device (example Such as, Microtrac MT 3000), with the ultrasonic wave of the output irradiation of 60W about 28kHz, and based on granularity point in measurement device Partial size at the 50% of cloth calculates average grain diameter (D50)。
The positive electrode active materials of embodiment according to the present invention can be prepared by the following method, which comprises By mixing cobalt raw material and lithium raw material with the amount for meeting the relational expression of 1≤Li/Co molar ratio, and carries out the first heating and prepare the The step of two lithium and cobalt oxides particles (step 1), and to the second lithium and cobalt oxides particle carry out more than one second plus Step (the step 2) of heat.According to another implementation of the invention, the preparation of cathode active material for lithium secondary battery is provided Method.
Hereinafter, each step will be described in detail, and step 1 is to prepare the step of the second lithium and cobalt oxides particle Suddenly.
Specifically, the second lithium and cobalt oxides particle can be by being mixed with the amount for meeting the relational expression of 1≤Li/Co molar ratio Cobalt raw material and lithium raw material, and the first heating is carried out to prepare.
In this case, cobalt raw material can be specially to contain cobalt/cobalt oxide, hydroxide, oxyhydroxide, halide, nitre Hydrochlorate, carbonate, acetate, oxalates, citrate or sulfate, and Co (OH) can be more specifically2、CoO、CoOOH、 Co(OCOCH3)2·4H2O、Co(NO3)2·6H2O or Co (SO4)2·7H2O, or can be their more than one mixture.
Lithium raw material can be specially oxide, hydroxide, oxyhydroxide, halide, nitrate, carbonic acid containing lithium Salt, acetate, oxalates, citrate or sulfate, and Li can be more specifically2CO3、LiNO3、LiNO2、LiOH、 LiOH·H2O、LiH、LiF、LiCl、LiBr、LiI、Li2O、Li2SO4、CH3COOLi or Li3C6H5O7, or can be their two Kind or more mixture.
Cobalt raw material and lithium raw material can be so that the amount for the relational expression that Li/Co molar ratio meets 1≤Li/Co molar ratio carry out Mixing.Using the combined amount range, the core of the lithium and cobalt oxides comprising the rich lithium with layer structure can be formed.More specifically Ground, it is contemplated that significant improvement, cobalt raw material and lithium raw material can be so that Li/Co molar ratio meet 1≤Li/Co molar ratio ≤ 1.2 relational expression, the amount of the relational expression of more specifically molar ratio≤1.1 1≤Li/Co are mixed.Furthermore it is possible to pass through So that Li/Co molar ratio can inject cobalt by the mode reduced in the range of 1≤Li/Co molar ratio≤1.2 at any time Raw material and lithium raw material obtain in the second lithium and cobalt oxides particle from the concentration of the reduced lithium concentration of the center to face of particle Gradient.
It, can be in mixing cobalt raw material and lithium raw material in the case where being doped to the second lithium and cobalt oxides being prepared The raw material for the metallic element (M ') that period, further selectively addition was used to adulterate.
The raw material of metallic element (M ') for doping can be specially selected from W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, At least one of Cr, Ba, Ca and Nb metal, or the oxide comprising it, hydroxide, oxyhydroxide, halide, nitric acid Salt, carbonate, acetate, oxalates, citrate or sulfate, or their two or more mixtures can be used.
The mixture of raw material first heating can 800 DEG C~1100 DEG C at a temperature of carry out.If heating temperature is small In 800 DEG C, then unreacted raw material may remain, and the discharge capacity of per unit weight may be decreased, and cycle performance It may deteriorate with operating voltage.If heating temperature is greater than 1100 DEG C, there may be by-product, and per unit weight is put Capacitance may be decreased, and cycle performance and operating voltage may deteriorate.
First heating can be preferably lower than the temperature for following second heating and temperature within the said temperature range Degree is lower to carry out, to be easy to control the diffusion rate of lithium.
In addition, the first heating can carry out 5 hours~30 hours in air or under oxygen atmosphere, so as to mixture grain Abundant diffusion reaction is carried out between son.
Then, poor lithium first is prepared in surface of the step 2 for the second lithium and cobalt oxides particle for preparing in step 1 The step of lithium and cobalt oxides.
Specifically, poor the first lithium and cobalt oxides of lithium can by 800 DEG C~1100 DEG C at a temperature of prepared in step 1 The second lithium and cobalt oxides particle carry out more than once, more specifically once to being specifically three times, further primary or two Secondary second heating is to prepare.It in this case, can be identical or different within the said temperature range for the temperature of each heating.
According in the lithium and air at the surface by being present in the second lithium and cobalt oxides particle during the second heating The reaction of oxygen and form lithia, first lithium and cobalt oxides of poor lithium can be formed.In addition, as the number of the second heating increases Add, the poor lithium in lithium and cobalt oxides can also increase, and as a result can form the center-to-face dimension mask from the first lithium and cobalt oxides There is the concentration gradient of the lithium concentration of reduction.
During the second heating, the property of can choose cobalt raw material or cobalt raw material and lithium raw material are further added.The material It all can once add, or in each step in the same amount or different amounts is gradually added respectively.
Specifically, in the case where only selectively further addition cobalt raw material, the cobalt and presence in cobalt raw material can be made Lithium at the surface of the second lithium and cobalt oxides particle is reacted, to generate the lithium cobalt of poor lithium of the Li/Co molar ratio less than 1 Oxide.In this case, cobalt raw material can be identical as those described above cobalt raw material, and can be suitable according to the concentration gradient of Li When the amount that control uses.
It, can be to meet molar ratio < 10 < Li/Co in the case where selectively further adding cobalt raw material and lithium raw material Or relational expression, the amount of the relational expression of more specifically molar ratio≤0.99 0.95≤Li/Co of molar ratio < 1 0.95≤Li/Co add Add cobalt raw material and lithium raw material.When mixing cobalt raw material and lithium raw material with above-mentioned amount range, the lithium cobalt oxide comprising poor lithium can be formed The layer of compound.In this case, cobalt raw material and lithium raw material can be identical as raw material those of described in step 1.
It, can be in mixing cobalt raw material and lithium raw material in the case where being doped to the first lithium and cobalt oxides being prepared The raw material for the metallic element (M) that period, selectively further addition was used to adulterate.
The raw material of metallic element (M) for doping can be specially selected from W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, Cr, At least one of Ba, Ca and Nb metal, or the oxide comprising it, hydroxide, oxyhydroxide, halide, nitrate, Carbonate, acetate, oxalates, citrate or sulfate, or their two or more mixtures can be used.
Meanwhile in step 2 second heating can 800 DEG C~1100 DEG C at a temperature of carry out.If heating temperature is small In 800 DEG C, then the crystallization of the lithium and cobalt oxides formed in surface may be carried out deficiently, and the transmission of lithium ion may It is suppressed.If heating temperature be greater than 1100 DEG C, crystallization may be carried out excessively, or due to the evaporation of Li in crystal structure and It is likely to form unstable structure.In step 2 second heating can preferably 1000 DEG C~1100 DEG C at a temperature of carry out, To prevent due to remaining unreacting material, the generation of by-product and the decrystallized and excessive crystalline substance of lithium and cobalt oxides that manufactures in this way The deterioration of the discharge capacity of per unit weight caused by changing and the deterioration of cycle performance and operating voltage.
Since the transmission and diffusion of lithium in active material can be promoted with the increase of the second heating temperature, The distribution of lithium can be controlled according to the second heating temperature in active material.Specifically, wherein in the temperature range In the case that second heating temperature is 1000 DEG C or more or 1000 DEG C~1100 DEG C, lithium can be in active material with concentration gradient Distribution.
In addition, the second heating can carry out 7 hours~50 hours in air or under oxygen atmosphere.If heating time Too long, then the evaporation of lithium and the crystallinity of the metal oxide layer formed on the surface can increase, so as to cause lithium ion Transmission is restricted.
The preparation method of the positive electrode active materials of embodiment is the dry method without using solvent according to the present invention.
Using solvent in the wet process for preparing positive electrode active materials and be surface-treated, metal precursor is being dissolved in solvent In after carry out using and the pH of solvent can be easily varied, and can be easy to change the positive-active material finally prepared The size of material, or may cause particle cracking.In addition, lithium ion may be dissolved out from the surface of the positive electrode active materials comprising lithium, And various oxides may be formed on the surface as by-product.On the contrary, positive electrode active materials can through the invention in Dry process can not generate the defect as caused by the use of solvent, and the preparation efficiency and processing performance of active material (process availability) can be good.In addition, according to the surface treatment carried out by dry method, without using bonding Agent can not generate the by-product as caused by the use of adhesive.
There are integrally-built lithium and cobalt oxides since the positive electrode active materials prepared by above-mentioned preparation method are included in The lithium and cobalt oxides with poor lithium structure at the surface side of particle, can be with by the lithium and cobalt oxides with poor lithium structure It is easy to carry out the insertion and deintercalation of lithium, therefore good output performance and multiplying power property can be obtained.In addition, because in particle Surface side in form poor lithium structure, so even if kinetically advantageous can also be obtained in case of large particle size Property, it is good output and discharge-rate performance.In addition, the increase of the size due to active material particles, can reduce specific surface Product, and due to the formation of poor lithium structure, it is possible to reduce the amount of lithium and cobalt oxides, therefore can reduce and be reacted with electrolyte Property, and the amount of the gas generated during battery operation can be reduced.
According to another implementation of the invention, anode and the secondary electricity of lithium comprising the positive electrode active materials are provided Pond.
Specifically, anode may include anode current collector and be formed in anode current collector and include positive electrode active materials Anode active material layer.
Anode current collector the chemical change for not causing battery can be used and conductive any material without Concrete restriction, and may include such as stainless steel, aluminium, nickel, titanium, burning carbon, or with carbon, nickel, titanium, silver etc. to aluminium or stainless steel The material that is surface-treated of surface.In general, anode current collector can have 3 μm~500 μm of thickness, and can be with Increase the adhesiveness of positive electrode active materials and forming micro concavo-convex on the surface in current-collector.It is, for example, possible to use include The various shape of film, piece, foil, net, porous body, foams, non-woven body etc..
Meanwhile anode active material layer can include conductive material and adhesive together with positive electrode active materials.At this In the case of kind, positive electrode active materials can be identical as the above material.
Conductive material will not cause the chemical change in battery and have for assigning electrode conductivuty, and can be used Any material of electronic conductivity is without especially limiting.Specific example may include graphite such as natural graphite and artificial graphite； Carbon materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal crack black and carbon fiber；Copper, nickel, aluminium, The metal powder or metallic fiber of silver etc.；Conductive whiskers such as zinc oxide and potassium titanate；Conductive metal oxide such as titanium oxide；Or Conducting polymer such as polyphenylene derivatives, and the material can be used alone or as their two or more mixing Object uses.In general, the total weight relative to anode active material layer, the content ratio of conductive material can be 1 weight % ~30 weight %.
Adhesive plays the adhesiveness improved between positive electrode active materials particle between positive electrode active materials and current-collector Effect.Specifically, it can be used that polyvinylidene fluoride (PVDF), (PVDF- is co- for vinylidene difluoride-hexafluoropropylene copolymer HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyethylene Base pyrrolidones, tetrafluoroethene, polyethylene, polypropylene, Ethylene-Propylene-Diene polymer (EPDM), sulfonated epdm, butylbenzene rubber Glue (SBR), fluorubber or their various copolymers, the material can be used alone or as the two or more of them Mixture uses.Relative to the total weight of anode active material layer, the content ratio of adhesive can be 1 weight of weight %~30 Measure %.
Anode with above structure can be manufactured by the commonsense method of manufacture anode, the difference is that using above-mentioned Positive electrode active materials.Specifically, the composition for being used to form anode active material layer can be coated in anode current collector, into Row drying, and rolling to manufacture anode active material layer, the composition for being used to form anode active material layer pass through by Positive electrode active materials, adhesive and conductive material dissolve and disperse to obtain in a solvent.In this case, positive-active material The type and amount of material, adhesive and conductive material can be identical as the above.
In addition, the solvent being used to form in the composition of anode active material layer can be usually used in this field molten Agent, and can be dimethyl sulfoxide (DMSO), isopropanol, N-Methyl pyrrolidone (NMP), acetone or water, and described molten Agent can be used alone or use as their two or more mixtures.In view of the coating thickness of slurry and manufacture produce Rate, if be coated after positive electrode active materials, conductive material and adhesive are dissolved or dispersed in solvent to manufacture During anode, composition has the viscosity for being capable of forming good the thickness uniformity, then the amount of the solvent used can be enough 's.
According to another method, anode can be manufactured by the way that following film layer to be pressed in anode current collector, the film passes through It is cast the composition of positive electrode active materials on individual support and separates and obtains with the support.
Another embodiment according to the present invention provides the electrochemical appliance comprising anode.The electrochemical appliance can To be specially battery or capacitor, and lithium secondary battery can be more specifically.
Lithium secondary battery may include anode, the cathode (negative electrode) in face of anode, setting in anode Diaphragm and electrolyte between cathode.The anode is same as described above.In addition, lithium secondary battery can be further selective Ground includes the battery case for receiving the electrode assembly of the positive electrode, the negative electrode and the separator, and the sealing structure for sealing the battery case Part.
In the lithium secondary battery, the cathode that cathode may include negative electrode current collector and be arranged in the negative electrode current collector Active material layer.
Negative electrode current collector can be the chemical change for not causing battery and conductive any material without special Limitation, and may include such as copper, stainless steel, aluminium, nickel, titanium, burning carbon, with carbon, nickel, titanium, silver etc. to copper or stainless steel The material or aluminium-cadmium alloy that surface is surface-treated.In general, negative electrode current collector can have 3 μm~500 μm of thickness Degree, and negative electrode active can be enhanced and forming micro concavo-convex on the surface in current-collector as in anode current collector The adhesiveness of material.It is, for example, possible to use the various shapes for including film, piece, foil, net, porous body, foams, non-woven body etc..
It together with negative electrode active material include the anode active material layer property of can choose adhesive and conductive material.It is negative Pole active material layer can for example manufacture in the following way: by the adhesive comprising negative electrode active material and selectivity and lead The composition for being used to form cathode of electric material is coated in negative electrode current collector, and is dried；Or it can be in the following way Manufacture: following film layer is pressed in negative electrode current collector, the film by individual support stream prolong and be used to form cathode Composition is simultaneously separated with the support and is obtained.
Negative electrode active material can be the compound for being able to carry out the reversible insertion and deintercalation of lithium.Specific example includes carbon Material such as artificial graphite, natural graphite, graphitized carbon fibre and amorphous carbon；The metallic compound of alloy can be formed such as with lithium Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy or Al alloy；The metal with dedoping lithium can be adulterated Oxide such as SiOx(0<x<2)、SnO2, vanadium oxide and lithium-barium oxide；Compound comprising metallic compound and carbon material is such as Si-C compound or Sn-C compound, and either of which kind or their two or more mixtures can be used.Separately Outside, lithium metal film can be used as negative electrode active material.As carbon material, the carbon with low-crystallinity can be used and have Both carbon of high-crystallinity.Carbon with low-crystallinity usually may include soft carbon and hard carbon, and the carbon with high-crystallinity is usual May include burning carbon under amorphous, plate, squamous, spherical or fibrous natural or artificial graphite and high temperature such as Kish, pyrolytic carbon, mesophase pitch-based carbon fibers, carbonaceous mesophase spherules, mesophase pitch and petroleum or coal tar asphalt Derivative coke.
Adhesive and conductive material can with those are identical shown in the explanation in anode.
Meanwhile cathode and anode are separated and provide lithium ion transport channel by the diaphragm in lithium secondary battery.Diaphragm can be with , without especially limiting, specifically, to have to the ion transmission in electrolyte used in any one of common lithium secondary battery The diaphragm of Low ESR and the impregnability with good electrolyte can be preferably.Specifically, porous polymeric can be used Object film, such as use polyolefin polymers such as Alathon, Noblen, ethylene/butylene copolymers, ethylene/hexene The apertured polymeric film or their two layers or more of layer structure of copolymer and the preparation of ethylene/methacrylic acid ester copolymer. Further, it is possible to use usually used perforated nonwoven fabrics, such as using with dystectic glass fibre, poly terephthalic acid second The non-woven fabrics of the formation such as terephthalate fibers.In addition it is possible to use the coating diaphragm comprising ceramic composition or polymer material is with true Protect heat resistance or mechanical strength, and the property of can choose use single layer structure or multilayered structure.
It is poly- that liquid organic electrolyte, inorganic liquid electrolyte, solid can be used in electrolyte used in the present invention Polymer electrolyte, gel-type polymer electrolyte, solid inorganic electrolytes, melting inorganic electrolyte etc. are without limiting.
Specifically, electrolyte may include organic solvent and lithium salts.
As organic solvent, can be used can play for transmitting the ion for the electrochemical reaction for participating in battery Medium effect any solvent without especially limiting.Specifically, organic solvent may include esters solvent such as acetic acid first Ester, ethyl acetate, gamma-butyrolacton and 6-caprolactone；Ether solvent such as butyl oxide and tetrahydrofuran；Ketones solvent such as cyclohexanone； Aromatic hydrocarbons solvent such as benzene and fluorobenzene；Carbonate-based solvent such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate Ester (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC) and propylene carbonate (PC)；Alcohols solvent such as ethyl alcohol and isopropyl Alcohol；Nitrile such as R-CN (wherein R be straight chain, branching or cyclic structure C2-C20 alkyl, and may include double bond aromatic rings or Ehter bond)；Amides such as dimethylformamide；Dioxolanes class such as 1,3- dioxolanes；Or sulfolane class.In these solvents, Carbonate solvent is preferred, the ring-type of high ion-conductivity and high dielectric property with the charge-discharge performance that can increase battery Carbonic ester (for example, ethylene carbonate or propylene carbonate) is with the linear carbonate compound with low viscosity (for example, carbonic acid second Methyl esters, dimethyl carbonate or diethyl carbonate) mixture be preferred.In this case, cyclic carbonate and linear Carbonic ester can be mixed with about 1:1~about 1:9 volume ratio, to obtain good electrolyte performance.
Lithium salts can be to be capable of providing any compound for the lithium ion in lithium secondary battery without especially limiting. Specifically, lithium salts may include: LiPF6、LiClO4、LiAsF6、LiBF4、LiSbF6、LiAlO4、LiAlCl4、LiCF3SO3、 LiC4F9SO3、LiN(C2F5SO3)2、LiN(C2F5SO2)2、LiN(CF3SO2)2, LiCl, LiI or LiB (C2O4)2.The concentration of lithium salts It can be in the range of 0.1M~2.0M.If the concentration of lithium salts is within the above range, electrolyte can have suitable biography The property led and viscosity, to provide effective transmission of good electrolyte performance and lithium ion.
In the electrolyte, other than the ingredient of electrolyte, for example halogenated carbonic acid of at least one additive can also be included Alkylidene ester type compound such as difluoro ethylene carbonate, pyridine, triethyl phosphite, triethanolamine, cyclic ethers, ethylenediamine, positive second Glycol dimethyl ether, hexamethylphosphoramide, nitrobenzene derivative, sulphur, quinoneimine dye, N- replaceOxazolidone, N, N- take Imidazolidine, glycol dialkyl ether, ammonium salt, pyrroles, 2-methyl cellosolve or the alchlor in generation, to improve the service life of battery Performance inhibits the capacity of battery to reduce, and improves the discharge capacity etc. of battery.Relative to the total weight of electrolyte, additive Content ratio can be 0.1 weight of weight %~5 %.
Lithium secondary battery containing a positive electrode active material according to the present invention has good discharge capacity and output performance, And stable capacity retention ratio, and mancarried device such as mobile phone, laptop and digital camera can be usefully used for And electric vehicle field including hybrid electric vehicle (HEV) etc..
According to another aspect of the present invention, it provides comprising lithium secondary battery as the battery module of element cell and comprising institute State the battery pack of battery module.
Battery module or battery pack may be used as following at least one medium-sized and large-scale plant power supply: electric tool； Electric vehicle class such as electric vehicle (EV), hybrid electric vehicle and plug-in hybrid electric vehicle (PHEV)；Or storage It can system.
It hereinafter, will the present invention will be described in more detail referring to following embodiment.However, embodiment may include respectively The different modifications of kind, and the scope of the present invention is not limited thereto.
[preparation example 1: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder is mixed with specific quantity, so that Li/Co molar ratio is in the range of 1.0~1.02 It gradually decreases with time going by, the first heating in 10 hours is then carried out at 900 DEG C.The powder mull that will be achieved in that And it is sieved to prepare the second lithium and cobalt oxides particle.
Relative to the second lithium and cobalt oxides particle being prepared, so that the specific quantity that Li/Co molar ratio is 0.95 is dry Mixed Li2CO3Powder and Co3O4Powder then carries out the second heating in 20 hours at 1050 DEG C, has overall structure with preparation Positive electrode active materials (average grain diameter: 10 μm), wherein lithium is dense with what is reduced from the center to face of particle in integral particles Spend gradient distribution.
[preparation example 2: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder is mixed with specific quantity so that Li/Co molar ratio be 1, then at 900 DEG C into Row heating in 10 hours is to prepare the second lithium and cobalt oxides particle.
The second lithium and cobalt oxides being prepared are heated 5 hours under oxygen atmosphere at 900 DEG C, and by the process Repeating 2 times has integrally-built positive electrode active materials (average grain diameter: 10 μm) with preparation, wherein with poor lithium structure Lithium and cobalt oxides are distributed in side on the surface of the particle with concentration gradient.
[preparation example 3: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder so that Li/Co molar ratio be 1 mode mix, then at 900 DEG C into Row heating in 10 hours, to prepare the second lithium and cobalt oxides particle.
The second lithium and cobalt oxides being prepared are heated 5 hours under oxygen atmosphere at 900 DEG C, and by the process Repeat 2 times.In each heating stepses, Co is injected with 0.05 mole and 0.25 mole of amount respectively3O4.As a result, being prepared for having There is integrally-built positive electrode active materials (average grain diameter: 10 μm), wherein the lithium and cobalt oxides with poor lithium structure are in particle It is distributed in surface side with concentration gradient.
[preparation example 4: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder is mixed with specific quantity, so that Li/Co molar ratio is 1.02, then at 900 DEG C Lower the first heating for carrying out 10 hours.By the powder mull being achieved in that and it is sieved to prepare the second lithium and cobalt oxides particle.
Relative to the second lithium and cobalt oxides particle being prepared, so that the specific quantity that Li/Co molar ratio is 0.95 is dry Mixed Li2CO3Powder and Co3O4Powder then carries out the second heating in 20 hours at 1050 DEG C, has overall structure with preparation Positive electrode active materials (average grain diameter: 12 μm), wherein lithium is dense with what is reduced from the center to face of particle in integral particles Spend gradient distribution.
[preparation example 5: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder is mixed with specific quantity so that Li/Co molar ratio be 1, then at 900 DEG C into First heating in row 10 hours.By the powder mull being achieved in that and it is sieved to prepare the second lithium and cobalt oxides particle.
Relative to the second lithium and cobalt oxides particle being prepared, so that the specific quantity that Li/Co molar ratio is 0.95 is dry Mixed Li2CO3Powder and Co3O4Powder then carries out the second heating in 20 hours at 900 DEG C, has with preparation integrally-built Positive electrode active materials (average grain diameter: 12 μm), wherein the first lithium and cobalt oxides with poor lithium structure include on the surface of the particle In side.
[preparation example 6: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder is mixed with specific quantity so that Li/Co molar ratio be 1, then at 900 DEG C into First heating in row 10 hours.By the powder mull being achieved in that and it is sieved to prepare the second lithium and cobalt oxides particle.
Relative to the second lithium and cobalt oxides particle being prepared, so that the specific quantity that Li/Co molar ratio is 0.95 is dry Mixed Li2CO3Powder and Co3O4Powder, and so that the amount of the Zr metal relative to 1 mole of Li is 0.01 mole specific In addition amount adds and mixes ZrO2Powder, then carries out the second heating in 20 hours at 1050 DEG C, has whole knot with preparation The positive electrode active materials (average grain diameter: 12 μm) of structure, wherein the lithium and cobalt oxides with poor lithium structure are on the surface of the particle in side It is distributed with concentration gradient, and the lithium and cobalt oxides with poor lithium structure are doped with Zr.
[preparation example 7: the preparation of positive electrode active materials]
By Li2CO3Powder and Co3O4Powder is mixed with specific quantity so that Li/Co molar ratio be 1, then at 900 DEG C into First heating in row 10 hours.By the powder mull being achieved in that and it is sieved to prepare the second lithium and cobalt oxides particle.
Relative to the second lithium and cobalt oxides particle being prepared, so that the specific quantity that Li/Co molar ratio is 0.95 is dry Mixed Li2CO3Powder and Co3O4Powder, and so that the amount of the Mg and Ti metal relative to 1 mole of Li is 0.01 mole In addition specific quantity adds respectively and mixes MgO and TiO2Powder carries out the second heating in 20 hours, at 1050 DEG C then with system It is standby that there is integrally-built positive electrode active materials (average grain diameter: 12 μm), wherein lithium in integral particles from the center of particle to Surface is distributed with reduced concentration gradient, and is included in doped with the first lithium and cobalt oxides with poor lithium structure of Mg and Ti In shell portion.
[Examples 1 to 7: the manufacture of lithium secondary battery]
Lithium secondary battery is manufactured using each positive electrode active materials prepared in preparation example 1~7.
Specifically, each positive electrode active materials, carbon black conductive material and PVdF adhesive that will be prepared in preparation example 1~7 Be blended in N-Methyl pyrrolidone solvent with the weight ratio of 90:5:5, with prepare be used to form anode composition (viscosity: 5000mPa·s).The composition is coated on aluminum current collector, dries and rolls to manufacture anode.
By as negative electrode active material and as the artificial graphite of carbonaceous mesophase spherules (MCMB), carbon black conductive material and PVdF adhesive is blended in N-Methyl pyrrolidone solvent with the weight ratio of 85:10:5, to prepare the group for being used to form cathode Close object.The composition is coated on copper collector, to manufacture cathode.
Porous polyethylene diaphragm is arranged between the positive electrode and negative electrode manufactured in this way to manufacture electrode assembly, and by the electricity Pole component is placed in shell.Electrolyte is injected into the shell to manufacture lithium secondary battery.In this case, by including carbonic acid Ethyl (EC)/dimethyl carbonate (DMC)/ethyl methyl carbonate (EMC) (volume ratio=3/4/3 of EC/DMC/EMC) is organic molten Lithium hexafluoro phosphate (the LiPF of 1.15M is dissolved in agent6) prepare electrolyte.
[comparative example 1: the manufacture of lithium secondary battery]
By carrying out manufacturing lithium secondary battery with identical process described in embodiment 1, the difference is that using LiCoO2(average grain diameter: 10 μm) is used as positive electrode active materials.
[comparative example 2: the manufacture of lithium secondary battery]
By Li2CO3Powder and Co3O4Powder with specific quantity mix so that Li/Co molar ratio be 1, then at 900 DEG C into First heating in row 10 hours.By the powder mull being achieved in that and it is sieved to prepare the second lithium and cobalt oxides particle.
Relative to the second lithium and cobalt oxides particle being prepared, so that the specific quantity that Li/Co molar ratio is 1.2 is dry-mixed Li2CO3Powder and Co3O4Powder then carries out the second heating in 20 hours at 1050 DEG C, includes and the second lithium cobalt with preparation Lithium concentration in the core of oxide particle compares the lithium and cobalt oxides (Li with high lithium concentration on the surface of the particleaCoO2, 0 < a ≤ 0.2) positive electrode active materials (average grain diameter: 10 μm).
[experimental example 1]
For the positive electrode active materials prepared in preparation example 1~5, basis is observed using x-ray photoelectron spectroscopy (XPS) From the surface of active material particles to the molar ratio variation of the Li/Co of internal depth distribution.As a result it is shown in the following table 1 and 2.
[table 1]
[table 2]
As shown in tables 1 and 2, the shell comprising the first lithium and cobalt oxides with poor lithium structure is corresponding to relative to work Property material particles radius from the distance rates that the surface of particle is started be 0.05~0.1 region in formed.
In addition, passing through the consecutive variations of the amount ratio of the material of control and the injection of heating temperature during preparation respectively To prepare the positive electrode active materials that wherein lithium is distributed in integral particles from the center to face of particle with reduced concentration gradient (preparation example 1 and 4) wherein has the lithium and cobalt oxides of poor lithium structure only in the table of particle by duplicate second heating to prepare The positive electrode active materials (preparation example 2 and 3) being distributed in surface side with concentration gradient, and prepare and do not have concentration in integral particles Gradient and only positive electrode active materials (preparation example 5) of the lithium and cobalt oxides in side comprising poor lithium on the surface of the particle.For system The preparation of the positive electrode active materials of standby example 3, repeats the second heating, and injection has with lithium one by one in each heating stepses Reactive cobalt oxide.Therefore, the thickness in the shell portion comprising poor lithium structure is larger, and in shell portion Li/Co molar ratio it is quick Variation.
[experimental example 2]
Using atom-probe sectional analysis art (APT) to the table of the particle of the lithium and cobalt oxides particle prepared in preparation example 2 Lithium distribution in surface side is observed.As a result shown in Figure 1.
In Fig. 1, a) show through the surface side of the lithium and cobalt oxides particle of the APT preparation example 2 observed (from particle Lithium distribution of the surface to center into 50mm), b) it is that the 3D information projection in a) at 2D and is measured into density and the photography that obtains Photo.
As shown in fig. 1, it can be confirmed that the density of lithium increases towards the center of lithium and cobalt oxides particle.Meanwhile in Fig. 1 The yellow richness lithium portion of upper right end is as caused by experimental error.
[experimental example 3]
Surface side and internal crystal structure to the active material of the lithium and cobalt oxides particle prepared in preparation example 2 into Row observation.As a result shown in Figure 2.
As shown in Figure 2, the tool of the first lithium and cobalt oxides (A) present in the surface side of lithium and cobalt oxides particle is identified There is cube type crystal structure of the Fd-3m space group as spinel type crystal structure.Meanwhile it identifying and being present in active material grain The second lithium and cobalt oxides (C) of the inside of son have the layered crystal structure of R_3m space group.
[experimental example 4]
It is (negative using Li metal using the positive electrode active materials manufacture coin battery prepared in preparation example 1 and comparative example 1 Pole), and charge and discharge are carried out to it under conditions of room temperature (25 DEG C) and 0.1C/0.1C.Then, initial charge/discharge performance is evaluated, And it shows the result in Fig. 3.
As shown in FIG. 3, compared with the positive electrode active materials without poor lithium structure of comparative example 1, in lithium cobalt oxidation The positive electrode active materials of preparation example 1 in the surface side of object particle, i.e. in shell portion with poor lithium structure show almost same journey The charge-discharge performance of degree.However, since there are poor lithium structures in shell portion, during charge and discharge 4.05V~4.15V it Between observe preparation example 1 positive electrode active materials voltage curve bending, i.e. inflection point.
[experimental example 5]
Under conditions of room temperature (25 DEG C) and 0.1C and 0.5C, prepared in preparation example 1 and comparative example 1 to using respectively The coin battery (use Li metal negative electrode) of positive electrode active materials manufacture carry out charge and discharge.Then, multiplying power property is evaluated.As a result It is shown in Figure 4.
As shown in Figure 4, with include do not have poor lithium structure LiCoO2Positive electrode active materials comparative example 1 lithium two Primary cell is compared, and includes that the lithium secondary battery of the positive electrode active materials of the preparation example 1 with poor lithium structure in shell has improvement Multiplying power property.
[experimental example 6]
The battery performance of the lithium secondary battery manufactured in Examples 1 and 2 and comparative example 1 is evaluated by the following method.
Specifically, for the lithium secondary battery manufactured in Examples 1 and 2 and comparative example 1, under room temperature (25 DEG C) The multiplying power property during charge and discharge is measured within the scope of the working voltage of 3V~4.4V under conditions of 2C/0.1C, and in high temperature Measure circulation under (60 DEG C) after 50 charge and discharge cycles under conditions of 0.5C/1C within the scope of the working voltage of 3V~4.4V Capacity retention ratio, i.e., ratio of the discharge capacity of the 50th time circulation relative to initial capacity.As a result it is shown in the following table 3.
[table 3]
From the experimental results, compared with the lithium and cobalt oxides comprising not having poor lithium structure are as positive electrode active materials The battery of example 1 is compared, and the battery of the Examples 1 and 2 comprising the lithium and cobalt oxides with poor lithium structure shows improved multiplying power Characteristic and life performance.
[experimental example 7: the evaluation of gas generating amount in lithium secondary battery]
Under high temperature (60 DEG C) within the scope of the working voltage of 3V~4.4V under conditions of 0.5C/1C, in embodiment 1 And the lithium secondary battery manufactured in comparative example 1 and 2 carries out 50 charge and discharge, and measures the gas generating amount in battery.Knot Fruit is shown in the following table 4.
[table 4]
Gas generating amount (μ l/mg)
Comparative example 1 3
Comparative example 2 5
Embodiment 1 1
From the experimental results, compared with the lithium and cobalt oxides comprising not having poor lithium structure are as positive electrode active materials The battery that the battery of example 1 is higher than the comparative example 2 of the lithium concentration in core with the lithium concentration in the lithium and cobalt oxides in wherein shell is compared, It include that the battery of the embodiment 1 of the lithium and cobalt oxides with poor lithium structure in shell has significantly reduced gas generating amount.

Claims (18)

1. a kind of cathode active material for lithium secondary battery, it includes lithium and cobalt oxides particle,
Wherein the lithium and cobalt oxides particle has the core-shell structure copolymer knot comprising core portion and the shell portion being arranged on the surface in the core portion Structure,
Wherein the lithium and cobalt oxides particle includes the lithium and cobalt oxides of the poor lithium on the surface of particle and following region, institute It states region and corresponds to and started from the surface of the particle from 0% to small relative to the distance r from the surface of the particle to center In 100% distance, the lithium and cobalt oxides of the poor lithium there is Li/Co molar ratio less than 1, belong to Fd-3m space group and With a cube type crystal structure,
Wherein the shell portion includes the first lithium and cobalt oxides of following formula 1, and
The core portion includes the second lithium and cobalt oxides of following formula 2:
[formula 1] Li1-aCoMxO2
[formula 2] LibCoM’yO2
In formula 1 and 2, M and M ' are each independently comprising in W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, Cr, Ba, Ca and Nb At least one metallic element, and a, b, x and y meet following relationship: 0 < a≤0.05,1≤b≤1.2,0≤x≤0.02, and 0≤y≤0.02。
2. positive electrode active materials according to claim 1, wherein
First lithium and cobalt oxides belong to Fd-3m space group and have cube type crystal structure, and
Second lithium and cobalt oxides have layered crystal structure.
3. positive electrode active materials according to claim 1, wherein the shell portion is following region, which corresponds to opposite In the distance from the surface of the lithium and cobalt oxides particle to center from the surface start from 0% to 99% distance.
4. positive electrode active materials according to claim 1, wherein the core portion and the shell portion have 1:0.01~1:0.1 Thickness ratio.
5. positive electrode active materials according to claim 1, wherein the core portion and the shell portion are respectively contained towards described The lithium that the center of lithium and cobalt oxides particle is distributed with increased concentration gradient.
6. positive electrode active materials according to claim 1, wherein the concentration gradient gradient of the lithium in the core portion and described The concentration gradient gradient of lithium in shell portion has identical or different value of slope.
7. positive electrode active materials according to claim 1, wherein the core portion has the lithium concentration higher than the shell portion, and And at least one of the core portion and the shell portion are included in corresponding region with lithium existing for a concentration value.
8. positive electrode active materials according to claim 1, wherein
The concentration gradient distribution that the lithium is gradually increased from the surface of the lithium and cobalt oxides particle to center, and
In formula 1 and 2, a is gradually reduced on the direction at the center towards the particle in the range of 0 < a≤0.05, and b exists It is gradually increased on the direction at the center towards the particle in the range of 1≤b≤1.2.
9. positive electrode active materials according to claim 1, wherein the positive electrode active materials have average grain diameter be 3 μm~ 50 μm of overall structure.
10. positive electrode active materials according to claim 1, when according to charge and discharge electrometric determination voltage curve, 4.0V~ There is inflection point in the voltage range of 4.2V.
11. a kind of method for the cathode active material for lithium secondary battery for preparing claim 1, which comprises
By mixing cobalt raw material and lithium raw material with the amount for meeting the molar ratio of 1≤Li/Co≤1.2, and the first heating is carried out, from And prepare the second lithium and cobalt oxides particle；And
The second more than one heating is carried out to the second lithium and cobalt oxides particle.
12. the method according to claim 11 for preparing cathode active material for lithium secondary battery, wherein described second In the preparation process of lithium and cobalt oxides particle, during mixing the cobalt raw material and the lithium raw material, further include containing choosing From the metalliferous raw material of at least one of W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, Cr, Ba, Ca and Nb metallic element.
13. the method according to claim 11 for preparing cathode active material for lithium secondary battery, wherein by air In atmosphere or oxygen atmosphere 800 DEG C~1100 DEG C at a temperature of heated and carry out it is described first heating.
14. the method according to claim 11 for preparing cathode active material for lithium secondary battery, wherein by air In atmosphere or oxygen atmosphere 800 DEG C~1100 DEG C at a temperature of heated and carry out it is described second heating.
15. the method according to claim 11 for preparing cathode active material for lithium secondary battery, wherein 800 DEG C~ Second heating twice is carried out at a temperature of 1100 DEG C, and the temperature during each heating is identical or different.
16. the method according to claim 11 for preparing cathode active material for lithium secondary battery, further include: described Cobalt raw material or cobalt raw material and lithium raw material are added during second heating.
17. the method according to claim 11 for preparing cathode active material for lithium secondary battery, further include: described Meet the amount addition cobalt raw material and lithium raw material of the relational expression of molar ratio < 1 0.95 < Li/Co during second heating.
18. the method according to claim 11 for preparing cathode active material for lithium secondary battery, further includes described Addition is comprising selected from least one of W, Mo, Zr, Ti, Mg, Ta, Al, Fe, V, Cr, Ba, Ca and Nb metal during second heating The metalliferous raw material of element.
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Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101787199B1 (en) * 2014-10-02 2017-10-18 주식회사 엘지화학 Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery comprising the same
CN105938917A (en) * 2016-07-01 2016-09-14 深圳市振华新材料股份有限公司 Lithium ion secondary cell lithium cobaltate cathode material, manufacture method and application thereof
KR102538830B1 (en) 2016-07-05 2023-05-31 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Cathode active material, manufacturing method of cathode active material, and secondary battery
KR102120271B1 (en) * 2016-09-01 2020-06-08 주식회사 엘지화학 Positive Electrode Active Material Comprising High-voltage Lithium Cobalt Oxide Having Doping element for Lithium Secondary Battery and Method of Manufacturing the Same
DE202017007645U1 (en) * 2016-10-12 2023-12-19 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material particles
KR20240046314A (en) 2017-05-12 2024-04-08 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Positive electrode active material particles
CN111900358A (en) 2017-05-19 2020-11-06 株式会社半导体能源研究所 Positive electrode active material and secondary battery
KR102223712B1 (en) 2017-06-26 2021-03-04 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Method for manufacturing positive electrode active material, and secondary battery
KR102335313B1 (en) * 2017-09-08 2021-12-06 주식회사 엘지에너지솔루션 Method for preparing positive electrode active material for lithium secondary battery, positive electrode active material prepared by the same and lithium secondary battery comprising the same
JP6812941B2 (en) * 2017-09-29 2021-01-13 トヨタ自動車株式会社 Positive electrode active material, positive electrode mixture, positive electrode active material manufacturing method, positive electrode manufacturing method, and oxide solid-state battery manufacturing method
JP7034275B2 (en) * 2017-10-20 2022-03-11 巴斯夫杉杉▲電▼池材料有限公司 Lithium-cobalt metal oxide powder, its preparation method, and method for determining the content of cobalt (II, III).
KR102165118B1 (en) * 2017-10-26 2020-10-14 주식회사 엘지화학 Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same
KR102500085B1 (en) 2017-10-26 2023-02-15 주식회사 엘지에너지솔루션 Positive Electrode Active Material Comprising Lithium Rich Lithium Manganese-based Oxide with Coating layer Comprising Lithium-Deficiency Transition Metal Oxide and Positive Electrode Comprising the Same
JP7062200B2 (en) 2017-11-13 2022-05-06 エルジー エナジー ソリューション リミテッド Lithium cobalt-based positive electrode active material, its manufacturing method, positive electrode including this, and secondary battery
WO2019103522A2 (en) * 2017-11-24 2019-05-31 주식회사 엘지화학 Method for preparing cathode active material
US11670754B2 (en) 2017-12-04 2023-06-06 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material
WO2019112279A2 (en) 2017-12-04 2019-06-13 삼성에스디아이 주식회사 Cathode active material for lithium secondary battery, manufacturing method therefor, and lithium secondary battery comprising cathode comprising same
US11777075B2 (en) 2017-12-04 2023-10-03 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material
US11522189B2 (en) 2017-12-04 2022-12-06 Samsung Sdi Co., Ltd. Positive electrode for rechargeable lithium battery, preparing method thereof, and rechargeable lithium battery comprising positive electrode
KR102424398B1 (en) 2020-09-24 2022-07-21 삼성에스디아이 주식회사 Positive electrode for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
KR102217766B1 (en) * 2017-12-11 2021-02-22 주식회사 엘지화학 Positive electrode active material for lithium secondary battery, preparing method of the same, positive electrode and lithium secondary battery including the same
CN113381000B (en) * 2018-05-18 2023-03-24 宁德新能源科技有限公司 Cathode material and lithium ion battery
KR102596885B1 (en) 2018-08-24 2023-10-31 주식회사 엘지에너지솔루션 Positive electrode active material for lithium rechargeable battery, method for manufacturing the same, and lithium rechargeable battery including the same
EP3900084A4 (en) * 2018-12-19 2022-10-12 Umicore Cobalt oxide as a precursor of positive electrode materials for rechargeable lithium ion batteries
WO2020154024A1 (en) * 2019-01-25 2020-07-30 Massachusetts Institute Of Technology Lithium transition metal oxide particles having lithium concentration gradients
KR102321251B1 (en) * 2019-09-09 2021-11-03 한국과학기술연구원 Cathode active material for sodium ion battery, and preparation process thereof
CN113809284B (en) * 2020-06-12 2023-09-05 比亚迪股份有限公司 Negative electrode material, preparation method thereof and all-solid-state lithium battery

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4106644B2 (en) 2000-04-04 2008-06-25 ソニー株式会社 Battery and manufacturing method thereof
US7138209B2 (en) * 2000-10-09 2006-11-21 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery and method of preparing same
JP2003217586A (en) * 2002-01-25 2003-07-31 Nec Tokin Tochigi Ltd Lithium ion secondary battery
KR20030083476A (en) 2002-04-23 2003-10-30 주식회사 엘지화학 Lithium metal oxides with enhanced cycle life and safety and a process for preparation thereof
CN1665052B (en) 2004-03-05 2013-04-03 日本化学工业株式会社 Lithium cobalt dioxide, preparing method thereof and non-aqueous electrolyte secondary battery
JP2006092820A (en) 2004-09-22 2006-04-06 Sanyo Electric Co Ltd Cathode active material for nonaqueous electrolyte secondary battery, cathode, and the nonaqueous electrolyte secondary battery
KR100738192B1 (en) * 2005-06-14 2007-07-10 에스케이 주식회사 Core-shell spinel cathode active materials for lithium secondary batteries, lithium secondary batteries using the same and Method for preparing thereof
EP1994587B1 (en) 2006-03-20 2018-07-11 LG Chem, Ltd. Stoichiometric lithium cobalt oxide and method for preparation of the same
JP5135912B2 (en) 2007-06-25 2013-02-06 三菱化学株式会社 Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery using the same
KR100889622B1 (en) 2007-10-29 2009-03-20 대정이엠(주) Cathode active material for lithium secondary batteries with high safety and method of preparing for the same and lithium secondary batteries comprising the same
US20100297686A1 (en) 2009-05-21 2010-11-25 Drexel University Devices for intracellular surface-enhanced raman spectroscopy
US8911902B2 (en) 2010-07-06 2014-12-16 Samsung Sdi Co., Ltd. Nickel-based positive electrode active material, method of preparing the same, and lithium battery using the nickel-based positive electrode active material
KR101215829B1 (en) 2010-07-22 2012-12-27 주식회사 에코프로 Manufacturing method of positive active material for lithium secondary battery, positive active material manufactured by the same and lithium secondary battery using positive active material
KR101292756B1 (en) * 2011-01-05 2013-08-02 한양대학교 산학협력단 Cathod active material, method for preparing the same, lithium secondary battery comprising the same
KR101316053B1 (en) 2011-04-26 2013-10-11 국립대학법인 울산과학기술대학교 산학협력단 Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
US9385368B2 (en) 2011-08-31 2016-07-05 3M Innovative Properties Company High capacity positive electrodes for use in lithium-ion electrochemical cells and methods of making same
KR20130033154A (en) 2011-09-26 2013-04-03 전자부품연구원 Positive active material, preparation method thereof and lithium secondary battery comprising the same
US20130171523A1 (en) 2011-12-28 2013-07-04 Zhi Chen Lithium-ion secondary battery and the cathode material thereof
CN102631875A (en) * 2012-03-19 2012-08-15 上海中兴派能能源科技有限公司 Multi-stage core and shell structure multi-element material, precursor thereof and preparation method for multi-stage core and shell multi-element material and precursor
KR102007411B1 (en) 2013-01-07 2019-10-01 삼성에스디아이 주식회사 Positive active material, positive electrode and lithium battery comprising the same, and method for preparation of the positive active material
KR20140095810A (en) 2013-01-25 2014-08-04 삼성에스디아이 주식회사 Positive active material for lithium secondary battery and lithium secondary battery
CN103715424B (en) 2014-01-06 2016-06-08 中国科学院宁波材料技术与工程研究所 A kind of nucleocapsid structure positive electrode and preparation method thereof
KR101787199B1 (en) 2014-10-02 2017-10-18 주식회사 엘지화학 Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery comprising the same

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